Methods of forming phase change memory with various grain sizes

ABSTRACT

A memory device includes a phase change element, which further includes a first phase change layer having a first grain size; and a second phase change layer over the first phase change layer. The first and the second phase change layers are depth-wise regions of the phase change element. The second phase change layer has a second average grain size different from the first average grain size.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of and claims the priority benefit ofU.S. patent application Ser. No. 13/029,436, filed on Feb. 17, 2011,which is a continuation of and claims the priority benefit of U.S.patent application Ser. No. 11/858,712, filed on Sep. 20, 2007, nowissued U.S. Pat. No. 7,893,420, and entitled “Phase Change Memory withVarious Grain Sizes,” the applications of which are hereby incorporatedherein by reference.

TECHNICAL FIELD

This invention relates generally to phase change memories, and moreparticularly to methods for improving the program reliability of phasechange memories.

BACKGROUND

Phase change technology is promising for next generation memories. Ituses chalcogenide semiconductors for storing states. The chalcogenidesemiconductors with phase change capability have a crystalline state andan amorphous state. In the crystalline state, the phase change materialshave low resistivities, while in the amorphous state they have highresistivities. The resistivity ratios of the phase change materials inthe amorphous and crystalline states are typically greater than 1000,and thus the resulting memory devices are unlikely to have errors forreading states. The chalcogenide materials are stable at certaintemperature ranges in both crystalline and amorphous states and can beswitched back and forth between the two states by electric pulses. Onetype of memory device that uses the principal of phase change inchalcogenide semiconductors is commonly referred to as phase changerandom access memory (PRAM).

Some phase change materials, such as Ge—Sb—Te alloys, may have threepossible structures, amorphous structure, face-centered cubic (FCC)structure, and hexagonal close packed (HCP) structure. Amorphous phasehas high resistivities, HCP phase has low resistivities, while FCC phasehas resistivities between the amorphous phase and the HCP phase.Typically, an amorphous phase change material may be transformed to theFCC phase change material at about 150° C., while transforming anamorphous phase or a FCC phase to HCP phase requires about 360° C. orhigher. Since the typical back end of processes require about 400° C.,the resulting phase change materials in phase change memories, asfabricated, are likely to be at the HCP state.

Since HCP phase change materials have low resistivities, the resetcurrent for the very first reset operation (initial reset operation)after the fabrication needs to be very high. In the subsequentoperations, the phases of phase change materials are typically switchedbetween the amorphous state and the FCC state. Therefore, the subsequentreset operations may be performed with smaller reset currents. However,the integrated circuits for providing reset currents need to support theinitial reset operation by providing high reset currents, although thesubsequent reset operations may only need smaller program currents. Thisis a serious issue for device operation. The reset current and also thedifference between initial and subsequent reset must be reduced.

To make things worse, since there are process variations in forming theheaters for heating the phase change materials, different phase changememory cells may need different reset currents even if they are in asame chip. Clearly, the initial reset currents need to be high enoughfor resetting all phase change memory cells. This further demands evenhigher initial reset currents, and hence putting a higher requirement tothe integrated circuits for providing the reset currents. In addition,power consumption is unnecessarily increased for non-initial resetoperations due to higher-than-necessary reset currents. New phase changememories and methods for forming the same are thus needed.

SUMMARY OF THE INVENTION

In accordance with one aspect of the present invention, a memory deviceincludes a phase change element, which further includes a first phasechange layer having a first grain size; and a second phase change layerover the first phase change layer. The first and the second phase changelayers are depth-wise regions of the phase change element. The secondphase change layer has a second average grain size different from thefirst average grain size.

In accordance with another aspect of the present invention, memorydevice includes a semiconductor substrate; a heater overlying thesemiconductor substrate; and a phase change element over thesemiconductor substrate. The phase change element is divided into atleast two substantially horizontal sub layers including a first sublayer adjoining the heater, wherein the first sub layer has a firstaverage grain size; and a second sub layer having a portion overlappingthe first sub layer, wherein the second sub layer has a second averagegrain size greater than the first average grain size.

In accordance with yet another aspect of the present invention, a memorydevice includes a semiconductor substrate having at least one activedevice formed thereon; a dielectric layer over the semiconductorsubstrate; a heater in the dielectric layer; a fine-grain crystallinephase change layer over the heater; a coarse-grain crystalline phasechange layer over the fine-grain crystalline phase change layer; and atop conductive layer over the coarse-grain crystalline phase changelayer.

In accordance with yet another aspect of the present invention, a memorydevice includes a semiconductor substrate; a conductive feature over thesemiconductor substrate; a dielectric layer over the conductive feature;a trench in the dielectric layer, wherein the conductive feature has atleast a portion exposed through the trench; and a phase change elementover the semiconductor substrate. The phase change element is dividedinto at least two substantially horizontal sub layers including a firstsub layer substantially limited to the trench, wherein the first sublayer has a first average grain size; and a second sub layer over thedielectric layer and the first sub layer, wherein the second sub layerhas a second average grain size greater than the first average grainsize.

In accordance with yet another aspect of the present invention, a methodfor forming a memory device includes providing a substrate; depositing afirst phase change layer over the substrate, wherein the first phasechange layer has a first average grain size; and depositing a secondphase change layer over the first phase change layer, wherein the secondphase change layer has a second average grain size different from thefirst grain size.

In accordance with yet another aspect of the present invention, a methodfor forming a memory device includes providing a substrate; forming aheater over the substrate; depositing a first phase change layer overand adjoining the heater using first process conditions; and depositinga second phase change layer using second process conditions differentfrom the first process conditions. The second phase change layer is overthe first phase change layer, and the first and the second phase changelayers are sub layers of a contiguous phase change layer.

The advantageous features of the present invention include reducedinitial reset current, and reduced difference between the initial resetcurrent, and subsequent reset currents.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present invention, and theadvantages thereof, reference is now made to the following descriptionstaken in conjunction with the accompanying drawings, in which:

FIGS. 1 through 9B are cross-sectional views of intermediate stages inthe manufacturing of phase change memories; and

FIGS. 9C, 10, and 11 illustrate cross-sectional views of additionalembodiments of the present invention.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The making and using of the presently preferred embodiments arediscussed in detail below. It should be appreciated, however, that thepresent invention provides many applicable inventive concepts that canbe embodied in a wide variety of specific contexts. The specificembodiments discussed are merely illustrative of specific ways to makeand use the invention, and do not limit the scope of the invention.

A novel phase change memory and the methods of forming the same areprovided. The intermediate stages of manufacturing preferred embodimentsof the present invention are illustrated. The variations of thepreferred embodiments are then discussed. Throughout the various viewsand illustrative embodiments of the present invention, like referencenumbers are used to designate like elements.

Referring to FIG. 1, conductive plug 22 is formed in dielectric layer24, which is further formed over semiconductor substrate 20.Semiconductor devices such as transistors (symbolized using transistor23) are formed at the surface of semiconductor substrate 20. Conductiveplug 22 may be formed of tungsten, aluminum, copper, silver, andcombinations thereof, and is electrically connected to the semiconductordevices. Dielectric layer 24 may be an inter-layer dielectric (ILD) oran inter-metal dielectric (IMD), and may be formed of materials havinglow k values, for example, with k values less than about 3.9. Conductiveplug 22 may be formed by forming an opening in dielectric layer 24,filling the opening with a conductive material, and performing achemical mechanical polish (CMP) to remove excess conductive material.For simplicity, semiconductor substrate 20 is not shown in subsequentdrawings.

In FIG. 2, crown oxide 26 is formed on dielectric layer 24, followed byforming opening 28 to expose the underlying conductive plug 22. Crownoxide 26 may be formed of essentially the same materials as low-kdielectric layer 24, or other commonly known dielectric materials suchas oxide, nitrides, oxynitrides, carbides, and the like.

Heater layer 30 is then blanket formed, followed by the formation ofdielectric layer 32, as is shown in FIG. 3. The materials in heaterlayer 30 may include conductive materials such as polysilicon, TiSiC, C,TiW, SiC, Ti, Ta, V, W, Cr, Fe, Ni, Nb, Pd, Pt, Zr, Mo, Cu, Al, Ag, Au,Hf, and alloys thereof. Alternatively, metal nitrides such as TiN, TaN,TiSiN, TiAlN, TiCN, TaSiN, MoN, TaAlN, and WN, metal silicides such asTiSix, NiSix, CoSix, conductive oxides such as IrO₂, RuO₂, SrRuO₃,LaNiO₃, and combinations thereof, can be used. In order to reduce thecontact area between the subsequently formed heater and phase changelayer, heater layer 30 is preferably thin, for example, with thicknessT1 less than about 200 Å. Dielectric layer 32 preferably fully fillsopening 28.

Referring to FIG. 4, a planarization is performed to remove excessheater layer 30 and dielectric layer 32. As a result, dielectric region36 is left in an inner region encircled by heater 34, and the edges 34′of heater 34 form a ring encircling dielectric region 36. Next, as isshown in FIG. 5, dielectric layer 38 is formed and patterned, formingtrench 40 therein. Through trench 40, a portion of dielectric region 36and at least one edge 34′ of heater 34 is exposed (refer to FIG. 6B).The width W of trench 40 is preferably small, for example, less thanabout 500 Å.

In FIG. 6A, fine-grain phase change layer 42 is formed to fill trench40. In the preferred embodiment, fine-grain phase change layer 42 isformed of GeSbTe (GST). Alternatively, fine-grain phase change layer 42may include Si—Sb—Te alloys, Ga—Sb—Te alloys, As—Sb—Te alloys,Ag—In—Sb—Te alloys, Ge—In—Sb—Te alloys, Ge—Sb alloys, Sb—Te alloys,Si—Sb alloys, and combinations thereof. As is known in the art, phasechange materials have a crystalline state with a low resistivity, and anamorphous state with a high resistivity. Preferably, thickness T2 offine-grain phase change layer 42 is greater than thickness T3 ofdielectric layer 38. More preferably, thickness T2 is greater than thethickness of the active region in the subsequently formed phase changeelement, wherein the active region is where phase change occurs. In anexemplary embodiment, thickness T2 is between about 200 Å and about 800Å. Presumably, the active region includes a portion of fine-grain phasechange layer 42 adjoining heater 34.

Fine-grain phase change layer 42 may have an average grain size ofbetween about 3 nm and about 10 nm, although it may have differentvalues. The smaller the grain size, the higher the resistivity andtransition temperature to HCP phase. The optimum grain size depends onthe preferred initial reset current (the very first reset currentapplied on the phase change memory cell after its operation), and thelower the desirable initial reset current, the smaller grain size ispreferred.

In an embodiment, the average grain size of fine-grain phase changelayer 42 is adjusted by adding impurities, such as nitrogen, oxygen,silicon, and combinations thereof, during its formation. Alternatively,dielectrics, for example, oxides such as silicon oxide and/or germaniumoxide, nitrides such as silicon nitride and/or germanium nitride, andoxynitrides such as silicon oxynitride, and/or germanium oxynitride maybe added. The formation of fine-grain phase change layer 42 may beperformed using reactive sputtering, co-sputtering, chemical vapordeposition, atomic layer deposition, and the like. In an exemplaryembodiment, a co-sputtering uses a GST target and a silicon target todope silicon into fine-grain phase change layer 42. The addition ofoxygen may be achieved by using oxygen-containing gases or using oxidetargets.

Preferably, if nitrogen, oxygen, and/or silicon are doped, the atomicpercentage of the dopants is between about 2% and 25%, while ifdielectrics are incorporated, the mole percentage of the dielectrics maybe between about 3% and 20%. It is realized that when more dopants ordielectrics are doped, the average grain size of fine-grain phase changelayer 42 is reduced, causing a decrease in grain size and an increase inthe resistivity. Accordingly, the reset current is reduced. Thecrystalline phase is stabilized, and the difference between the initialreset current and subsequent reset currents is reduced.

Alternatively, fine-grain phase change layer 42 is formed by adjustingthe deposition temperature. Reducing deposition temperatures cause theaverage grain sizes to be smaller. Conversely, increasing depositiontemperatures causes the average grain sizes to be greater. In anexemplary embodiment, the deposition of fine-grain phase change layer 42is performed at a temperature of less than about 250° C.

FIG. 6B shows a cross-sectional view of the structure shown in FIG. 6A,wherein the cross-sectional view is taken along a plane crossing line6B-6B in FIG. 6A. It indicates that the portion of fine-grain phasechange layer 42 formed in trench opening 40 (refer to FIG. 5) is incontact with the top edge of heater 34, wherein the active region 43will be the portion of fine-grain phase change layer 42 adjoining thecorresponding interface. Preferably, after reset operations, activeregion 43 becomes amorphous. Optionally, fine-grain phase change layer42 may extend to the left and contact both edges of heater 34, althoughthis scheme causes an increase in the contact area between heater 34 andfine-grain phase change layer 42.

FIG. 6C illustrates an optional CMP step to level the top surfaces offine-grain phase change layer 42 and dielectric layer 38. In thisembodiment, thickness T2 of the remaining portion of fine-grain phasechange layer 42 is preferably greater than about 150 Å, or at leastgreater than the thickness of the resulting active region.

Next, as shown in FIG. 7, the formation process is changed to formcoarse-grain phase change layer 44, which has a greater average grainsize than that of fine-grain phase change layer 42. Preferably, a ratioof the average grain size of coarse-grain phase change layer 44 to theaverage grain size of fine-grain phase change layer 42 is greater thanabout two. In an exemplary embodiment, the average grain size ofcoarse-grain phase change layer 44 is between about 6 nm and about 20nm. Coarse-grain phase change layer 44 preferably has a thicknessgreater than about 200 Å. Fine-grain phase change layer 42 andcoarse-grain phase change layer 44 are preferably formed of a same phasechange material, although they can be formed of different materials.Throughout the description, phase change layers 42 and 44 are referredto as depth-wise regions due to the fact that they are formed layer bylayer, and hence are at different depths of the respective wafer.

Similar to what is discussed in the preceding paragraphs, the grain sizeof coarse-grain phase change layer 44 may be adjusted by adding dopants,such as nitrogen, oxygen, silicon, and dielectrics including oxides,nitrides, oxynitrides, and the like. The percentage of the dopants incoarse-grain phase change layer 44 is thus accordingly less than infine-grain phase change layer 42. Alternatively, the average grain sizeof coarse-grain phase change layer 44 is increased by increasingdeposition temperatures, and exemplary deposition temperatures aregreater than about 300° C. Experimental data has revealed that withdeposition temperatures of less than about 250° C. and greater thanabout 300° C., the resistivities of fine-grain phase change layer 42 andcoarse-grain phase change layer 44 (which are both formed of GST) mayhave desirable values.

In the preferred embodiment, the formations of coarse-grain phase changelayer 44 and fine-grain phase change layer 42 are in-situ performed,preferably without vacuum break. In an embodiment, after fine-grainphase change layer 42 is formed, the process conditions are changed tothe process conditions for forming coarse-grain phase change layer 44,and then the deposition is started again. As a result, phase changelayers 42 and 44 have a relatively abrupt interface. Alternatively, thedeposition continues during the gradual transition of the processconditions, and thus the deposited phase change materials graduallychanges from fine grain to coarse grain. Naturally, even if the processconditions are abruptly changed and the transitions are abrupt, a thintransition layer will be formed. Clearly, the grain size in thetransition layer will be between the grain sizes of the fine-grain andcoarse-grain phase change layers 42 and 44.

FIG. 8 illustrates the formation of top electrode 46, which may includeTi, TiN, TiW, W, TiAl, TiAlN, Ta, TaN, W, and the like.

FIG. 9A illustrates the formation of top electrode contact 48, which maybe formed of conductive material having low resistivities. A phasechange memory cell is thus formed. In FIGS. 6A through 9A, dielectricmaterials need to be formed to define the boundaries of layers 38, 42,44, 46, and 48. These dielectric materials are omitted in the drawings.One skilled in the art will realize their formation details.

FIG. 9B illustrates a resulting memory cell formed based on thestructure shown in FIG. 6C, wherein fine-grain phase change layer 42 islimited to the trench defined by dielectric layer 38. In FIG. 9C, nodielectric layer 38 is formed, and thus the interface between fine-grainphase change layer 42 and heater 34 forms a ring.

FIG. 10 illustrates a T-shaped memory cell, wherein fine-grain phasechange layer 42 is in contact with a pillar-like heater 34. In FIG. 11,bottom electrode 50 is formed under fine-grain phase change layer 42.Bottom electrode 50, fine-grain phase change layer 42, coarse-grainphase change layer 44, and top electrode 46 all have pillar shapes andare formed between metal lines 52 and 54. One skilled in the art willrealize that phase change memory cells may have many different forms.

After the back end of the process is finished, fine-grain phase changelayer 42 and coarse-grain phase change layer 44 may have same ordifferent crystalline structures, with each including face-centeredcubic (FCC) structure, hexagonal close packed structure (HCP) structure,or combinations thereof. At the HCP state, phase change materials havelower resistivities than at the FCC state. Fine-grain phase change layer42 is more likely to have more FCC structures than coarse-grain phasechange layer 44. It is also likely that fine-grain phase change layer 42is formed substantially entirely of FCC structures, while coarse-grainphase change layer comprises FCC structures and HCP structures.Advantageously, by forming fine-grain phase change layer 42, theinterfacial free energy is increased due to the increased grain boundaryarea between grains. This causes the transition temperature of the HCPstate to be increased. Preferably, the transition temperature isincreased higher than the temperatures adopted by the back end of theprocess. Accordingly, in the resulting phase change memories, fine-grainphase change layers are less likely to be transitioned to the HCP state,and the initial resistivities of the phase change memories areincreased. Advantageously, this reduces the required initial resetcurrents, and hence the difference between the initial reset current andsubsequent reset currents.

Simulation has been performed to fabricate three sample memory cellswith similar structures, wherein the first and the second samples areformed of coarse-grain and fine-grain phase change materials, while thethird sample (an embodiment of the present invention) includes acoarse-grain layer and a fine-grain layer. Simulation results have shownthat the first sample needs an initial reset current of about 585 μA,the second sample needs an initial reset current of about 97 μA, whilethe third sample requires an initial reset current of about 100 μA.Compared to the first sample, the third sample needs a much lowerinitial reset current. Compared to the second sample, the third samplehas the advantageous features of reducing voltage drop on the phasechange memory cell due to the existence of coarse-grain phase changelayer 44.

Although the present invention and its advantages have been described indetail, it should be understood that various changes, substitutions, andalterations can be made herein without departing from the spirit andscope of the invention as defined by the appended claims. Moreover, thescope of the present application is not intended to be limited to theparticular embodiments of the process, machine, manufacture, andcomposition of matter, means, methods, and steps described in thespecification. As one of ordinary skill in the art will readilyappreciate from the disclosure of the present invention, processes,machines, manufacture, compositions of matter, means, methods, or steps,presently existing or later to be developed, that perform substantiallythe same function or achieve substantially the same result as thecorresponding embodiments described herein may be utilized according tothe present invention. Accordingly, the appended claims are intended toinclude within their scope such processes, machines, manufacture,compositions of matter, means, methods, or steps.

What is claimed is:
 1. A method of forming a memory device comprising: forming a cup shaped heater element, the cup having a ring shaped top surface; forming a patterned dielectric layer over the cup shaped heater element, the patterned dielectric layer having a trench therein exposing a portion of the ring shaped top surface while leaving covered a second portion of the ring shaped top surface; forming a fine grain phase change layer in the trench and in contact with the exposed portion of the ring shaped top surface; and forming a coarse grain phase change layer on the fine grain phase change layer.
 2. The method of claim 1 wherein the fine grain phase change layer contacts the entire ring shaped top surface.
 3. The method of claim 1 wherein the fine grain phase change layer is formed in a trench in a dielectric layer overlying the heater element.
 4. A method of forming a memory device comprising: forming over a substrate a heater element; depositing on at least a portion of the heater element a fine grain phase change layer; planarizing a top surface of the fine grain phase change layer; depositing on the fine grain phase change layer a coarse grain phase change layer; and forming an electrical contact to the coarse phase change layer or the heater element or both.
 5. The method of claim 4 wherein forming over a substrate a heater element comprises: forming a heater element layer along a bottom and sidewalls of a trench.
 6. The method of claim 5 further comprising: forming a dielectric layer over the substrate; removing a region of the dielectric layer to form a trench therein; depositing the heater element layer along the bottom and sidewalls of the trench and along the top of the dielectric layer; and planarizing the heater element layer to a top surface of the dielectric layer.
 7. The method of claim 5 further comprising: forming a dielectric layer over the substrate; removing a region of the dielectric layer to form a trench therein; depositing the heater element layer along the bottom and sidewalls of the trench and along the top of the dielectric layer; depositing a second dielectric layer atop the heater element layer and within a hollow formed by the heater element layer; and planarizing the heater element layer and the second dielectric layer to a top surface of the dielectric layer.
 8. The method of claim 4 wherein the steps of depositing on at least a portion of the heater element a fine grain phase change layer, and depositing on the fine grain phase change layer a coarse grain phase change layer, comprising depositing both layers in-situ without vacuum break.
 9. The method of claim 4 wherein the fine grain phase change layer is deposited with a first percentage of dopant impurity added during deposition and the coarse grain phase change layer is deposited with a second percentage of dopant impurity added during deposition, the second percentage being less than the first percentage.
 10. The method of claim 4 wherein the fine grain phase change layer is deposited with at a first deposition temperature and the coarse grain phase change layer is deposited with at a second deposition temperature, the second temperature being greater than the first temperature.
 11. The method of claim 9 wherein both the fine grain phase change layer and the coarse grain phase change layer is deposited with a dopant impurity selected from the group consisting of: nitrogen, oxygen, silicon, oxides of silicon, oxides of germanium, oxynitrides of silicon, oxynitrides of germanium, and combinations thereof.
 12. A method of forming a memory device comprising: forming a transistor on a substrate; forming a conductive feature in a first dielectric layer above the substrate; forming a crown oxide on the first dielectric layer and conductive feature; patterning the crown dielectric to form a trench therein, the trench exposing the conductive feature; conformally forming a heater element layer over the crown dielectric and in the trench, wherein the heater element layer electrically contacts the conductive feature and defines a ring structure having a hollow defined therein; filling the hollow by forming a second dielectric layer in the hollow and over the heater element layer; planarizing the second dielectric and the heater element layer to a top surface of the crown oxide, forming a heater element having a ring structure in a plane parallel to a major surface of the substrate and a remaining crown dielectric portion within the ring structure; depositing a third dielectric over heater element and the remaining crown dielectric portion and forming a trench in the third dielectric, wherein the trench exposes at least one sidewall of the ring structure; depositing a fine grain phase change layer in the trench, wherein the fine grain phase change layer electrically contacts the at least one sidewall of the ring structure; depositing a coarse grain phase change layer on the fine grain phase change layer; and forming an electrical contact on the coarse grain phase change layer.
 13. The method of claim 12 wherein the fine grain phase change layer and the coarse grain phase change layer are deposited in-situ without a vacuum break.
 14. The method of claim 12 further comprising planarizing the fine grain phase change layer before depositing the coarse grain phase change layer.
 15. The method of claim 12 wherein the step of depositing a fine grain phase change layer comprises sputter depositing a phase change material.
 16. The method of claim 15 wherein the stop of depositing a fine grain phase change layer further comprises co-sputtering a GeSbTe target and a Si target to dope the fine grain phase change layer with a silicon dopant.
 17. The method of claim 12 wherein the step of depositing a fine grain phase change layer comprises depositing a material selected from the group consisting of GeSbTe, Si—Sb—Te alloys, Ga—Sb—Te alloys, As—Sb—Te alloys, Ag—In—Sb—Te alloys, Ge—In—Sb—Te alloys, Ge—Sb alloys, Sb—Te alloys, Si—Sb alloys, and combinations thereof.
 18. The method of claim 12 wherein the fine grain phase change alloy is doped with an impurity at an atomic percentage of from about 2% to about 25%.
 19. The method of claim 12 wherein the step of the step of depositing a fine grain phase change layer is performed at a deposition temperature of less than about 250° C. and the step of depositing a coarse grain phase change layer on the fine grain phase change layer is performed at a deposition temperature of greater than about 300° C.
 20. The method of claim 12 further comprising a transitional layer between the fine grain phase change layer and the coarse grain phase change layer. 